CN102839354A - Preparation method for component-controlled ZrOx thin film - Google Patents
Preparation method for component-controlled ZrOx thin film Download PDFInfo
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- CN102839354A CN102839354A CN2012103741571A CN201210374157A CN102839354A CN 102839354 A CN102839354 A CN 102839354A CN 2012103741571 A CN2012103741571 A CN 2012103741571A CN 201210374157 A CN201210374157 A CN 201210374157A CN 102839354 A CN102839354 A CN 102839354A
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Abstract
The invention belongs to the technical field of spinning semiconductor materials, in particular relates to a preparation method for component-controlled ZrOx thin film. According to the preparation method, metal zirconium with purity of 4N serves as a target material, the flow ratio of oxygen gas serving as reaction gas to argon gas serving as working gas is controlled to change the content of oxygen of the prepared ZrOx thin film, the purity of the oxygen gas and the argon gas are 5N, and the representative flow ratio O2: Ar is equal to (4,6,8): 35sccm. According to test result, the ZrOx thin film having different components is changed from paramagnetism to ferromagnetism with the increase of oxygen content, and the ZrOx having the characteristics has high potential application value.
Description
Technical field
The invention belongs to the spin technical field of semiconductor, be specifically related to a kind of ZrO of controllable components
xThe preparation method of film.
Background technology
Semiconductor science plays a crucial role in the science and technology breakthrough development in last century with technology; It has promoted the develop rapidly of Materials science and modern technologies; Cause revolutionary change and breakthrough in many technical fields, greatly promoted science and technology and even social progress.Yet the size of large-scale integrated circuit is more and more littler at present, and traditional microelectronic technique can not satisfy existing to the ever-increasing requirement of equipment integrationization, more can not adapt to the development trend of modern information technologies ultra-high speed, ultra-high frequency and vast capacity.Given this, people begin to pay close attention to material-diluted magnetic semiconductor of possessing magnetic and characteristic of semiconductor simultaneously (Diluted Magnetic Semiconductors, DMS).DMS typically refers in compound semiconductors such as II-VI family, IV-VI family, II-V family, III-V family, by 3
dMagnesium-yttrium-transition metal or 4
fRare earth ion partly substitutes non magnetic positively charged ion and one type of new function material forming.Dilute magnetic semiconductor has magneto-optic, the magnetic electricity performance of multiple excellence; Make it wide application prospect arranged, therefore caused people's very big concern and research enthusiasm in fields such as high-density nonvolatile memory, magnetic inductor, SIC, semiconductor laser and spinning electron computingmachines.
DMS Development of Materials history can be traced back to the end of the sixties in last century, rare earth doped Eu
2+Rock salt structure compound and spinel structure compound just as magneticsemiconductor and by extensive studies.But these compound structures are complicated, and the preparation of its monocrystalline and processing is difficulty very; And its Tc T
C50
KAbout in addition lower; Therefore, the magneticsemiconductor of these rock salt structure compounds and spinel structure compound is mainly used in the research of fundamental research and concept type device, does not have practical value.Up to the end of the eighties in last century, people have found to have caused the revolution of area information storage thus by giant magnetoresistance effect when the research magnetoresistance effect, make the DMS material obtain people's attention gradually.Along with the development of material epitaxy technology, the non-equilibrium growth technique of low temperature of molecular beam epitaxy technique (MBE) makes the content of magnetic impurity can break through the restriction of solubleness, and magnetic components reaches the requirement of DMS to magnetic ion concentration in the material thereby make.1989, this method of humans such as Munekata InMnAs film of successfully having grown, and in p type InMnAs film, found ferromegnetism.Afterwards, people such as Ohno had successfully prepared the GaMnAs (T with higher curie transition temperature in 1992
C=110
K), therefore once appearance, just received the extensive concern of various countries' researchers, and risen a upsurge of taking turns thus for DMS research.
The magnetic source that a focus of paying close attention in the DMS research is a system.Because 3
dTransition metal itself and related compound all might deposit form so-called " second phase " in the preparation process, thus the source of its magnetic of interferometric analysis.A kind of method in clear and definite magnetic source is to carry out meticulous structure and performance test analysis.A kind of in addition method is to select nonmagnetic elements to mix or non-doping, because nonmagnetic elements itself and related compound generally do not have ferromegnetism, if observe the ferromegnetism of room temperature in the system, then can think it must is its intrinsic attribute.
ZIRCONIUM DIOXIDE 99.5 (ZrO
2) film has many good physical propertiess: leakage current is little, Heat stability is good, its chemical structure be less than 1000 ℃ the time; No matter be in vacuum or in nitrogen, can both keep stable, has the energy gap of higher insulating coefficient (10 ~ 80), high specific refractory power, broad, very low or the like to the photonic absorbance of wavelength region 300 ~ 1100 nm.Because the not available various advantageous properties of other MOX, ZrO are arranged
2Be widely used in various optical thin films, particularly the application in MOS in recent years (especially being used as gate dielectric) receives very big attention, and therefore the characteristic research to the ZIRCONIUM DIOXIDE 99.5 film has great practical value.2007, Ostanin found through Theoretical Calculation, ZrO
2Under suitable Mn mixes, can obtain the ferromegnetism of room temperature.If also can obtain room-temperature ferromagnetic experimentally, can in the application of expansion zirconium white in the spin semiconducter device, step major step undoubtedly.
Summary of the invention
The object of the present invention is to provide a kind of ZrO of controllable components
xMethod for manufacturing thin film, and to this ZrO
xThe physical properties of film is studied.
The ZrO of controllable components provided by the invention
xMethod for manufacturing thin film is to utilize high vacuum magnetic control sputter coating system, employing purity be the metal zirconium of 4N (99.99 %) as target, through the throughput ratio of control reactant gases oxygen, change and prepare ZrO with the working gas argon gas
xThe content of oxygen element in the film.Test result shows, along with the increase of oxygen level, ZrO
xFilm generation paramagnetism is to ferromagnetic transformation.Promptly control O suitable in the preparation process
2Oxygen argon throughput ratio: Ar=(4～8): 35 sccm, when oxygen argon throughput ratio is O
2: Ar=(4～6): during 35 sccm, the ZrO of acquisition
xThe physical properties of film is a paramagnetism, when oxygen argon throughput ratio is O
2: during Ar=6～8:35 sccm, the ZrO of acquisition
xThe physical properties of film progressively changes ferromegnetism into.
Below specify ZrO of the present invention
xThe preparation method of film, the control of component and corresponding test analysis means.
The metal zirconium target purity that the present invention adopted is 4N.In the coating process, adopting silicon single crystal Si (100) substrate is substrate, and the background vacuum pressure is 6.0 * 10
-6Mbar, working gas are high-purity argon and high purity oxygen (5N, 99.999 %), and operating air pressure is 4.0 * 10
-3Mbar.Be stability, the controllability of guaranteeing preparation condition, the present invention fixedly is being prepared as follows condition: under the room temperature, the sputtering power of fixing metal Zr target is 150
W, the background vacuum pressure is 6.0 * 10
-6Mbar, working gas are high-purity argon and high purity oxygen (5N), and operating air pressure is 4.0 * 10
-3On the basis of mbar, only regulate and control oxygen argon throughput ratio O through changing oxygen flow
2: Ar=(4～8): (representational oxygen argon throughput ratio is O to 35 sccm among the embodiment
2: Ar=(4,6,8): 35 sccm), to realize to ZrO
xEffective control of oxygen element content in the film.Thereby obtain according to the required ZrO of design requirements
xFilm.
To ZrO by above method preparation
xThe composition analysis of film, microstructure analysis and magnetism characteristic test thereof adopt x-ray photoelectron power spectrum (XPS), X-ray diffraction (XRD) and superconductive quantum interference survey meter (SQUID) to realize testing respectively.
The X-ray photoelectron spectroscopic analysis method is to utilize the lower x-ray source of energy as excitaton source; With the sample surfaces atomic interaction after; The intratomic shell electron is excited ionization; Through the electronics that analytic sample emits, realize a kind of surface analysis technique of analytic sample chemical ingredients with characteristic energy.Its analytical element wide ranges can be analyzed all elements beyond the dehydrogenation in principle; Analysis depth is more shallow, greatly 25～100 scopes below the surface; Its absolute sensitivity is very high, is a kind of ultramicro-analysis technology.Therefore, employing should technology to ZrO
xThe composition of film is analyzed, and can obtain zr element and oxygen element percentage composition in this film sample more exactly.
The constitutional features of analysis of material and the preparation condition of material are the Basic Ways that obtains material character to effect on structure.Utilize the ZrO of X-ray diffractometer experiments of measuring preparation
xFilm sample structure, diffraction angle sweep limit are from 10.0 ° to 65.0 °, and sweep velocity is 2 °/min, and step-length is 0.02 °.
Will be by the ZrO of design requirements preparation
xFilm sample uses superconductive quantum interference survey meter (SQUID) to carry out the measurement of magnetism characteristic.The SQUID magnetometer is the dc magnetizing strength of high-acruracy survey material in very wide temperature magnetic field range and the system of ac magnetization intensity.
Description of drawings
Fig. 1 is the ZrO of preparation attitude
xThe XRD figure spectrum of film sample.Wherein, (111) diffraction peak of m (111) expression oblique system ZIRCONIUM DIOXIDE 99.5; Si (200) is (200) diffraction peak of silicon substrate.
Fig. 2 is the ZrO of preparation attitude
xThe wide range XPS figure of film sample.Wherein, Zr 4p, Zr 4s, Zr 3d, Zr 3p
3/2, Zr 3p
1/2, Zr 3s representes 4p, 4s, 3d, the 3p of zirconium respectively
3/2, 3p
1/2, power spectrum peak that each electronic state of 3s is corresponding, O1s representes the corresponding power spectrum peak of 1s attitude of oxygen, the KLL auger peak of O (KLL) expression oxygen.
Fig. 3 is the ZrO of preparation attitude
xThe zr element XPS of film sample combines power spectrum.Wherein: Zr
iThe corresponding spectrum of the interstitial defect peak of expression zirconium, Zr
4+3d
3/2, Zr
4+3d
5/2The 3d that representes 4+ valency zirconium respectively
3/2And 3d
5/2The power spectrum peak that electronic state is corresponding, Zr
3+, Zr
2+The 3+ valence state power spectrum peak corresponding of representing zirconium respectively with the 2+ valence state.
Fig. 4 is the ZrO of preparation attitude
xThe oxygen element XPS of film sample combines power spectrum.Wherein: ZrO/Zr
2O
3Represent the power spectrum peak that a zirconium white is corresponding with zirconium sesquioxide, O
Zr/ O
iThe corresponding spectrum peak of interstitial defect of the antistructure defect of expression oxygen and oxygen, O1s representes the corresponding power spectrum peak of 1s attitude of oxygen.
Fig. 5 is the ZrO of preparation attitude
xThe room temperature SQUID collection of illustrative plates of film sample.Wherein: T=300 K representes measuring result at room temperature.
ZO-1, ZO-2, ZO-3 among all figure is the film sample numbering of preparation.
Embodiment
Use the LAB600sp magnetic control sputtering system, adopt high-purity (4N) metallic Z r as target.In the experiment, the sputtering power of fixing metal Zr target is 150
W, working gas argon stream amount is set at 35
Sccm, and oxygen flow is respectively 4
Sccm, 6
SccmWith 8
Sccm, change ZrO with this
xOxygen element content in the film sample.The background vacuum pressure is 6.0 * 10
-6Mbar, working gas are high-purity argon (5N) and high purity oxygen (5N), and operating air pressure is 4.0 * 10
-3Mbar.Three kinds of representative ZrO that prepare under the above condition
xFilm sample, its parameter and numbering are listed in the table below 1.
The ZrO for preparing under table 1 different condition
xFilm sample and zirconium oxygen element percentage composition thereof
。
Utilize the ZrO of X-ray diffractometer experiments of measuring preparation
xFilm sample structure, diffraction angle sweep limit are from 10.0 ° to 65.0 °, and sweep velocity is 2 °/min, and step-length is 0.02 °.It is as shown in Figure 1 to measure the gained result.As can be seen from the figure, be 4 at oxygen flow
Sccm, 6
SccmWith 8
SccmThe film of following preparation has only monoclinic ZrO
2The generation that other is miscellaneous is not found at (111) peak.
X-ray photoelectron power spectrum (XPS) is to confirm the component and the valent state of its material through the electronics bound energy of measuring element in the material.In the research of diluted semi-conductor thin-film, people often confirm the valence state of element in the film sample through XPS measuring, pay special attention to detect the metal cluster whether zero-valent state is arranged and exist.Measuring result is like Fig. 2,3, shown in 4.From the XPS figure of wide range, can see, except zirconium white, not find the appearance of other impurity element in the film sample, not observe tangible peak in the zone that especially transition metal element (iron, cobalt, nickel) exists between 600eV～900eV.Can find among Fig. 3 that bound energy is respectively 185.6eV and the 183.4eV place is respectively Zr
4+Zr 3
d 3/2With Zr 3
d 5/2The peak.In addition, three film samples have all been found the low price (Zr of Zr at the low energy place
2+, Zr
3+) go back ortho states, promptly reduction reaction has all taken place in three film samples in the preparation process.Fig. 4 is O 1
sXps energy spectrum figure, than film sample ZO-1 and ZO-2, a tangible peak has appearred in sample ZO-3 at the low energy place, we think that oxygen antistructure defect that the zirconium atom position forms causes owing to Sauerstoffatom more than needed occupies this peak.
Fig. 5 is the room temperature magnetic hysteresis loop that obtains after three film samples adopt SQUID to measure.From figure, can be clear that film sample ZO-1 and ZO-2 show as tangible paramagnetic characteristic; And along with the increase of oxygen level, the ZO-3 sample shows as the hysteresis of tangible ferromagnetic material, shows that this sample is ferromagnetic in room temperature.Therefore, the ZrO that obtains through magnetron sputtering
xFilm sample has taken place by the transformation of paramagnetic characteristic to ferromagnetic characteristic with the increase of oxygen level.Magnetic source for non-adulterated MOX based diluted magnetic semiconductor exists a lot of disputes at present always.Most of research groups propose, and its magnetic possibly derive from the pollution of the magneticmetal group that introduces in the specimen preparation process bunch or its two second phase.And this experiment can clearly be got rid of the possibility that other metallic element exists from XRD and XPS result.Therefore, we think the ZrO to this Experiment Preparation
xThe magnetic source of film should be the intrinsic property that its film itself is had.Can know that in conjunction with the XRD that records, XPS, the further analysis of SQUID spectrogram the ferromegnetism of sample ZO-3 film derives from the antistructure defect of the oxygen of introducing in the specimen preparation process.
Claims (2)
1. the ZrO of a controllable components
xThe preparation method of film is characterized in that utilizing high vacuum magnetic control sputter coating system, adopt purity be the metal zirconium of 4N as target, fixedly be prepared as follows condition: room temperature, the sputtering power of fixing metal Zr target is 150
W, the background vacuum pressure is 6.0 * 10
-6Mbar, working gas are high-purity argon and high purity oxygen, and operating air pressure is 4.0 * 10
-3Mbar through the throughput ratio of control reactant gases oxygen and working gas argon gas, changes preparation ZrO
xThe content of oxygen element in the film, promptly controlling oxygen argon throughput ratio is O
2: Ar=(4～8): 35 sccm, when oxygen argon throughput ratio is O
2: Ar=(4～6): during 35 sccm, the ZrO of acquisition
xThe physical properties of film is a paramagnetism, when oxygen argon throughput ratio is O
2: during Ar=6～8:35 sccm, the ZrO of acquisition
xThe physical properties of film progressively changes ferromegnetism into.
2. the ZrO of controllable components according to claim 1
xThe preparation method of film, it is characterized in that controlling oxygen argon throughput ratio is O
2: Ar=(4,6): during 35 sccm, the ZrO of acquisition
xThe physical properties of film is a paramagnetism, and control oxygen argon throughput ratio is O
2: during Ar=8:35 sccm, the ZrO of acquisition
xThe physical properties of film is a ferromegnetism.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108431292A (en) * | 2015-12-23 | 2018-08-21 | 万腾荣先进材料德国有限责任公司 | Sputtering target material based on zirconium oxide |
| CN112028120A (en) * | 2019-12-30 | 2020-12-04 | 有研资源环境技术研究院(北京)有限公司 | ZrO for plating optical thin filmxAnd method for preparing the same |
| CN116283278A (en) * | 2023-02-20 | 2023-06-23 | 深圳市翔通光电技术有限公司 | Zirconium oxide and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108431292A (en) * | 2015-12-23 | 2018-08-21 | 万腾荣先进材料德国有限责任公司 | Sputtering target material based on zirconium oxide |
| CN108431292B (en) * | 2015-12-23 | 2020-04-21 | 万腾荣先进材料德国有限责任公司 | Zirconia-based sputtering target |
| CN112028120A (en) * | 2019-12-30 | 2020-12-04 | 有研资源环境技术研究院(北京)有限公司 | ZrO for plating optical thin filmxAnd method for preparing the same |
| CN112028120B (en) * | 2019-12-30 | 2023-01-06 | 有研资源环境技术研究院(北京)有限公司 | ZrO for plating optical thin film x And method for preparing the same |
| CN116283278A (en) * | 2023-02-20 | 2023-06-23 | 深圳市翔通光电技术有限公司 | Zirconium oxide and preparation method thereof |
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Application publication date: 20121226 |